KR20200089965A - New β-selenylated ketone derivatives and Synthetic method thereof - Google Patents

New β-selenylated ketone derivatives and Synthetic method thereof Download PDF

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KR20200089965A
KR20200089965A KR1020190006903A KR20190006903A KR20200089965A KR 20200089965 A KR20200089965 A KR 20200089965A KR 1020190006903 A KR1020190006903 A KR 1020190006903A KR 20190006903 A KR20190006903 A KR 20190006903A KR 20200089965 A KR20200089965 A KR 20200089965A
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methyl
cyclopentanone
phenylselanyl
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KR102149415B1 (en
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김대영
김연주
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순천향대학교 산학협력단
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    • C—CHEMISTRY; METALLURGY
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    • C07C391/00—Compounds containing selenium
    • C07C391/02—Compounds containing selenium having selenium atoms bound to carbon atoms of six-membered aromatic rings
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    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J19/087—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
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Abstract

The present invention relates to a novel β-selenylated ketone derivative and a method for preparing the same. The preparation method of the present invention has been developed for the first time in the world by introducing a functional group of a diselenide derivative to an allyl alcohol derivative to allow semi-pinacol rearrangement to occur. In particular, by introducing the functional groups of allyl alcohol derivatives and diselenide derivatives and allowing the semi-pinacol rearrangement to proceed, using an electrochemical method, it is possible to synthesize β-selenylated ketone derivatives which are various derivatives in high yield (up to 90%), even under mild and environmentally friendly conditions.

Description

신규한 베타 셀레닐 케톤 유도체 및 이의 제조방법 {New β-selenylated ketone derivatives and Synthetic method thereof}New β-selenylated ketone derivatives and Synthetic method thereof

본 발명은 신규한 베타 셀레닐 케톤 유도체 및 이의 제조방법에 관한 것으로서, 구체적으로는 알릴알코올 유도체 (allylalcohol derivatives)로부터 유기 전기화학 방법을 이용하여 베타 셀레닐 케톤 유도체를 제조하는 방법으로서, 다양한 약리학적 특성을 가진 유기 셀레늄 작용기를 알릴알코올 유도체에 도입시킨 후 세미-피나콜 전이 반응을 거쳐 베타 셀레닐 케톤 유도체를 효율적이고 친환경적으로 제조하는 방법에 관한 것이다.The present invention relates to a novel beta selenyl ketone derivative and a method for manufacturing the same, specifically, a method for manufacturing a beta selenyl ketone derivative using an organic electrochemical method from allyl alcohol derivatives (allylalcohol derivatives), various pharmacological After introducing an organic selenium functional group having properties to an allyl alcohol derivative, a semi-finacol transfer reaction is carried out to provide an efficient and eco-friendly method for producing a beta selenyl ketone derivative.

셀레닐(selenyl, Se) 작용기를 갖는 화합물들은 특별한 생물학적, 화학적 성질 때문에 의약품, 농약 및 물질 산업에서 매우 중요하며 다양한 의약품으로서 개발되고 있다. 그 예로, 여러 가지 셀레늄 치환 acyclouridine 유도체는 HIV-1 (LAV 균주)에 감염된 사람 말초 혈액 단핵구 (PBM) 세포에서 항바이러스 활성을 갖는 것으로 연구되었다. 또한, 셀레닐 작용기를 갖는 화합물들로서 항암제, 항산화제, 항염증제, 효소와 같은 광범위하고 흥미로운 약리학적 특성을 가진 다양한 약물 후보 및 생체 활성 화합물들이 널리 알려져 있다 (그림1). 이러한 화합물의 광범위한 적용 때문에 새로운 유기 셀레늄 화합물 및 이의 새롭고 실용적인 합성 방법 개발이 많은 관심을 받고 있다.Compounds having selenyl (Se) functional groups are very important in the pharmaceutical, agrochemical and substance industries due to their special biological and chemical properties, and are being developed as various pharmaceutical products. For example, several selenium-substituted acyclouridine derivatives have been studied to have antiviral activity in human peripheral blood monocyte (PBM) cells infected with HIV-1 (LAV strain). In addition, various drug candidates and bioactive compounds with broad and interesting pharmacological properties such as anticancer agents, antioxidants, anti-inflammatory agents, and enzymes are widely known as compounds having a selenyl functional group (Fig. 1). Due to the wide application of these compounds, the development of new organic selenium compounds and their new and practical synthetic methods has attracted much attention.

또한, 유기 분자의 합성에 전기 화학적 방법을 적용하는 것은 지난 수십 년 동안 많은 시도가 이루어져 이 분야에서 큰 부흥과 발전이 이루어졌다. 생태 학적 측면에서도 전기화학의 산화 환원 시약을 전기로 대체하는 것에 의하여 친환경적으로 유기 분자를 합성할 수 있게 되는 장점이 있다. 유기 분자 합성 시, 반응 진행에 필요한 전자의 첨가 또는 제거가 전류의 사용으로 이루어지므로 통상적으로 유기 합성 시 전자의 첨가 또는 제거를 위하여 사용되던 종래의 시약 사용을 피할 수 있게 되고, 이에 따라 유기 폐기물의 발생을 피하여 친환경적이며, 전체적으로 반응시약의 사용을 감소시켜 경제적인 측면에서도 우수한 장점을 가진다.In addition, the application of electrochemical methods to the synthesis of organic molecules has undergone many attempts over the past few decades, with great revival and development in this area. The ecological aspect also has the advantage of being able to synthesize organic molecules in an environmentally friendly manner by replacing the redox reagent of electrochemistry with electricity. When synthesizing organic molecules, the addition or removal of electrons necessary for the progress of the reaction is made by the use of electric current, so it is possible to avoid the use of conventional reagents used for the addition or removal of electrons during organic synthesis. It is eco-friendly by avoiding occurrence, and has the advantage of economical efficiency by reducing the use of reagents as a whole.

Figure pat00001
Figure pat00001

그림 1. 생리활성 유기 셀레늄 화합물의 예Figure 1. Examples of bioactive organic selenium compounds

본 발명에서는 알릴알코올 유도체 (allylalcohol derivatives)로부터 베타 셀레닐 케톤 유도체를 효율적으로 제조하여 신규한 베타 셀레닐 케톤 유도체 및 이의 제조방법을 제공하고자 하는 것이다. In the present invention, it is intended to provide a novel beta selenyl ketone derivative and a method for producing the beta selenyl ketone derivative efficiently from allyl alcohol derivatives.

종래에 알릴알코올 유도체로부터 베타 위치에 작용기(치환기)가 있는 케톤 유도체를 합성하는 제조방법들이 알려져 있으나 작용기(치환기)로서 셀레닐기가 도입된 제조방법은 알려져 있지 않다. 또한, 베타 위치에 작용기(치환기)가 있는 케톤 유도체를 합성하는 제조방법의 반응 방법에 있어서도 종래에는 광촉매 반응이나 금속 촉매, 산화제를 이용하는 반응 방법은 알려져 있었으나 전기화학 반응을 통하여 알릴알코올에 작용기(치환기)를 도입시킨 후 세미-피나콜 전이 반응을 진행하는 반응 방법은 지금까지 알려져 있지 아니하다.Conventionally, there are known production methods for synthesizing ketone derivatives having a functional group (substituent) at the beta position from an allyl alcohol derivative, but a production method in which selenyl group is introduced as a functional group (substituent) is not known. Further, in the reaction method of the production method for synthesizing a ketone derivative having a functional group (substituent) at the beta position, a reaction method using a photocatalytic reaction, a metal catalyst, or an oxidizing agent has been known in the prior art, but a functional group (substituent) for allyl alcohol through an electrochemical reaction The reaction method of introducing semi-finacol transfer reaction after the introduction of) is not known so far.

따라서 본 발명의 구체적인 목적은 전기화학을 이용하여 알릴알코올 유도체로부터 베타 셀레닐 케톤 유도체를 온화하고 친환경적인 조건에서 효율적으로 높은 수율로 제조할 수 있도록 한 베타 셀레닐 케톤 유도체 및 이의 제조방법을 제공하는 데 있다. Accordingly, a specific object of the present invention is to provide a beta-selenyl ketone derivative and a method for manufacturing the beta-selenyl ketone derivative from an allyl alcohol derivative using an electrochemistry in an efficient and high-yield condition under mild and eco-friendly conditions. Having

상기 목적을 달성하기 위하여 본 발명에 따른 베타 셀레닐 케톤 유도체의 제조방법은, 탄소 전극 하에서 전해질 n-Bu4NBF4을 이용하여, 알릴알코올 유도체에 다이셀레나이드 유도체를 이용하여 셀레닐기 도입 후 세미-피나콜 전이반응을 진행 시키는 것을 특징으로 한다.In order to achieve the above object, a method for producing a beta-selenyl ketone derivative according to the present invention is a semi-after the introduction of a selenyl group using a di-selenide derivative in an allyl alcohol derivative using an electrolyte n- Bu 4 NBF 4 under a carbon electrode. -It is characterized in that the progress of the pinacol transfer reaction.

상술한 바와 같이, 본 발명에 따르면, 전기화학을 이용하여 알릴알코올 유도체로부터 높은 수율 얻어지는 신규한 베타 셀레닐 케톤 유도체를 제공할 수 있다. As described above, according to the present invention, it is possible to provide a novel beta selenyl ketone derivative obtained in high yield from an allyl alcohol derivative using electrochemistry.

또한, 본 발명에 따르면, 최초로 전기화학을 이용하여 작용기로서 다이셀레나이드를 사용하여 베타 셀레닐 케톤 유도체를 온화한 조건에서 높은 수율로 효율적으로 합성할 수 있는 장점을 가진다. In addition, according to the present invention, it has the advantage of being able to efficiently synthesize beta-selenyl ketone derivatives at high yields under mild conditions by using diselenide as a functional group using electrochemistry for the first time.

본 발명의 상기 및 그 밖의 목적과 새로운 특징은 본 명세서에 의하여 더욱 명확해질 것이다.The above and other objects and new features of the present invention will be further clarified by the present specification.

먼저 본 발명에 따른 베타 셀레닐 케톤 유도체의 제조방법의 특징에 관하여 설명한다. First, features of the method for preparing a beta-selenyl ketone derivative according to the present invention will be described.

본 발명에서는 전기화학을 이용하여 알릴알코올 유도체로부터 다이셀레나이드를 사용하여 베타 셀레닐 케톤 유도체를 온화한 조건에서 높은 수율로 효율적으로 제조할 수 있다. In the present invention, beta-selenyl ketone derivatives can be efficiently produced in high yields under mild conditions using di- selenide from allyl alcohol derivatives using electrochemistry.

본 발명의 일 실시 예에 따른 베타 셀레닐 케톤 유도체의 제조방법은 하기 [반응식 1]과 같이 용매 하에서 유리 탄소 전극을 이용하여 알릴알코올 유도체 (allylalcohol derivatives, 화학식1)에 다이셀레나이드 유도체 (diselenide derivatives, 화학식 2)를 이용하여 작용기를 도입하고 세미-피나콜 전이반응을 진행하여 베타 셀레닐 케톤 유도체 [화학식 3]를 제조하는 방법이다. The method for preparing a beta-selenyl ketone derivative according to an embodiment of the present invention is a diselenide derivatives in an allyl alcohol derivative (allylalcohol derivatives, formula 1) using a free carbon electrode under a solvent as shown in [Reaction Scheme 1] , By introducing the functional group using the formula (2) It is a method of preparing a beta-selenyl ketone derivative [Formula 3] by performing a semi-finacol transfer reaction.

더욱 구체적으로 상기 [화학식 3]의 베타 셀레닐 케톤 유도체 제조방법은 우선 알릴알코올 유도체, 다이셀레나이드 유도체 및 n-Bu4NBF4를 혼합한 후, 이 혼합물에 아세트니트릴 용매를 가하여 얻어진 혼합액에 유리 탄소 전극을 넣고 IKA ElectraSyn 기기에서 5 내지 10 mA의 전류로 30분 이상 2시간미만 동안 교반 하여 반응 시키는 것이다.More specifically, the method for preparing a beta-selenyl ketone derivative of [Formula 3] is first mixed with an allyl alcohol derivative, a di-selenide derivative, and n-Bu 4 NBF 4 , and then added to the mixture to give an acetonitrile solvent. The carbon electrode is put in and reacted by stirring for 5 minutes or more and less than 2 hours at a current of 5 to 10 mA in an IKA ElectraSyn device.

[반응식 1][Scheme 1]

Figure pat00002
Figure pat00002

(상기 [반응식 1]에서 상기 R1는 C1-C3 알콕시기, 알킬기, 할로겐 원소로 치환된 아릴기이고, 특히 나프틸기, 페닐기 또는 벤질기이다. R2는 페닐기 또는 벤질기이다)(In [Scheme 1], R 1 is a C1-C3 alkoxy group, an alkyl group, an aryl group substituted with a halogen element, and is particularly a naphthyl group, a phenyl group, or a benzyl group. R 2 is a phenyl group or a benzyl group)

상기 [반응식 1]의 제조방법에 사용되는 알릴알코올 유도체는 하기 [화학식 1]의 구조를 갖는다.The allyl alcohol derivative used in the preparation method of [Scheme 1] has the structure of [Chemical Formula 1].

[화학식 1][Formula 1]

Figure pat00003
Figure pat00003

(상기 [화학식 1]에서 상기 R1은 C1-C3 알콕시기, 알킬기, 할로겐 원소로 치환된 아릴기이고, 특히 나프틸기, 페닐기 또는 벤질기이다)(In [Formula 1], R1 is a C1-C3 alkoxy group, an alkyl group, an aryl group substituted with a halogen element, and particularly a naphthyl group, a phenyl group, or a benzyl group)

상기 [반응식 1]의 제조방법에 사용되는 다이셀레나이드 유도체는 하기 [화학식 2]의 구조를 갖는다.The die selenide derivative used in the preparation method of [Scheme 1] has the structure of [Chemical Formula 2].

[화학식 2][Formula 2]

Figure pat00004
Figure pat00004

(상기 [화학식 2]에서 상기 R2는 페닐기 또는 벤질기이다)(In [Formula 2], R2 is a phenyl group or a benzyl group)

상기 [반응식 1]의 제조방법에 의하여 합성된 베타 셀레닐 케톤 유도체는 하기 [화학식 3]의 구조를 갖는다.The beta selenyl ketone derivative synthesized by the method of [Scheme 1] has the structure of [Chemical Formula 3].

[화학식 3][Formula 3]

Figure pat00005
Figure pat00005

(위 [화학식 3]의 R1, R2는 위에서 정의한 바와 같다)(R 1 and R 2 in the above [Formula 3] are as defined above)

이하, 하기 실시 예 등에 의하여 본 발명을 더욱 상세하게 설명하고자 한다. 다만, 하기 실시 예 등은 본 발명을 예시하기 위한 것일 뿐 본 발명의 범위가 이들만으로 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail by the following examples. However, the following examples are only intended to illustrate the present invention and the scope of the present invention is not limited to them.

본 발명의 바람직한 일 실시예에 따라, 상기 [반응식 1]과 같이, 아세토나이트릴 용매와 전해질 n-Bu4NBF4하에서 탄소 전극을 사용하여 상기 [화학식 1]의 구조를 갖는 알릴알코올 유도체에 상기 [화학식 2]의 구조를 갖는 다이셀레나이드 유도체를 이용하여 작용기를 도입하고 세미-피나콜 전이 반응을 진행하여 상기 [화학식 3]으로 나타내는 베타 셀레닐 케톤 유도체를 합성하였으며 그 결과를 [표 1]에 나타내었다. 이때 [표1]은 [표1]a로 표기할 수 있으며, a는 isolated yield를 의미한다.According to one preferred embodiment of the present invention, as in [Scheme 1], using an carbon electrode under acetonitrile solvent and electrolyte n -Bu 4 NBF 4 to the allyl alcohol derivative having the structure of [Formula 1] The functional group was introduced using a di- selenide derivative having the structure of [Formula 2] and a semi-finacol transfer reaction was performed to synthesize the beta-selenyl ketone derivative represented by [Formula 3], and the results were shown in [Table 1]. It is shown in. In this case, [Table 1] can be written as [Table 1] a , where a is It means isolated yield.

Figure pat00006
Figure pat00006

[실시예 1][Example 1]

2-phenyl-2-((phenylselanyl)methyl)cyclopentanone (3a)2-phenyl-2-((phenylselanyl)methyl)cyclopentanone (3a)

Figure pat00007
Figure pat00007

반응 플라스크에 1-(1-aryllvinyl)cyclobutanol (0.1 mmol) [화학식 1], diphenyl diselenide (0.2 mmol) [화학식 2] 및 n-Bu4NBF4 (0.2mmol)를 넣는다. 그 후 아세토나이트릴 2mL를 넣는다. 유리 탄소 전극을 넣고 IKA ElectraSyn 기기에서 7 mA의 전류로 1시간 동안 상온 교반 한다. TLC 확인 후 반응 진행이 완료되면, ethyl acetate 10mL, 증류수 10mL 넣고 두 번 추출한다. 그 후 유기층을 Na2SO4로 탈수한다. 감압 필터 후 감압 농축하여 얻어진 반응혼합물을 SiO2컬럼 크로마토그래피 ethyl acetate : n-hexane = 1 : 10으로 분리, 정제하여 상기 [표1]의 화합물(3a)을 얻었다.To the reaction flask, 1-(1-aryllvinyl)cyclobutanol (0.1 mmol) [Formula 1], diphenyl diselenide (0.2 mmol) [Formula 2] and n- Bu 4 NBF 4 (0.2 mmol) are added. Then, add 2 mL of acetonitrile. Insert the glass carbon electrode and stir at room temperature for 1 hour at a current of 7 mA in an IKA ElectraSyn device. After the TLC is confirmed, when the reaction is complete, 10 mL of ethyl acetate and 10 mL of distilled water are added and extracted twice. Thereafter, the organic layer is dehydrated with Na 2 SO 4 . The reaction mixture obtained by concentrating under reduced pressure after filtering under reduced pressure was separated and purified by SiO 2 column chromatography ethyl acetate: n -hexane = 1: 10 to obtain compound (3a) of [Table 1].

Yield: 90%; yellow oil; 1H-NMR (400 MHz, CDCl3) δ 7.42-7.37 (m, 4H), 7.34-7.30 (m, 2H), 7.27-7.23 (m, 1H), 7.21-7.18 (m, 3H), 3.39 (d, J = 12 Hz, 1H), 3.30 (d, J = 12.4 Hz, 1H), 2.70-2.65 (m, 1H), 2.40-2.20 (m, 3H), 2.00-1.90 (m, 1H), 1.84-1.73 (m, 1H); 13C-NMR (100 MHz, CDCl3) δ 217.9, 138.4, 132.6, 131.0, 128.9, 128.7, 127.4, 126.8, 126.7, 57.8, 37.8, 37.4, 33.6, 18.4. Yield: 90%; yellow oil; 1 H-NMR (400 MHz, CDCl 3 ) δ 7.42-7.37 (m, 4H), 7.34-7.30 (m, 2H), 7.27-7.23 (m, 1H), 7.21-7.18 (m, 3H), 3.39 ( d, J = 12 Hz, 1H), 3.30 (d, J = 12.4 Hz, 1H), 2.70-2.65 (m, 1H), 2.40-2.20 (m, 3H), 2.00-1.90 (m, 1H), 1.84 -1.73 (m, 1H); 13 C-NMR (100 MHz, CDCl 3 ) δ 217.9, 138.4, 132.6, 131.0, 128.9, 128.7, 127.4, 126.8, 126.7, 57.8, 37.8, 37.4, 33.6, 18.4.

[실시예 2][Example 2]

실시예 1 중 [화학식 1] 이외에는 실시예 1과 동일한 방법으로 진행하여 상기 [표1]의 화합물(3b)를 얻었다.The compound (3b) of [Table 1] was obtained in the same manner as in Example 1 except for [Formula 1] in Example 1.

2-((phenylselanyl)methyl)-2-(p-tolyl)cyclopentanone (3b)2-((phenylselanyl)methyl)-2-(p-tolyl)cyclopentanone (3b)

Figure pat00008
Figure pat00008

Yield: 81%; pale oil; 1H-NMR (400 MHz,CDCl3) δ 7.41-7.38 (m, 2H), 7.30-7.28 (m, 2H), 7.20-7.18 (m, 3H), 7.14-7.12 (m, 2H), 3.39 (d, J = 12.4 Hz, 1H), 3.28 (d, J = 12.4 Hz, 1H), 2.68-2.64 (M, 1H), 2.37-2.15 (m, 6H), 1.98-1.90 (m, 1H), 1.83-1.71 (m, 1H); 13C-NMR (100 MHz, CDCl3) δ 218.0,137.2, 135.3, 132.5, 131.0, 129.4, 128.9, 126.7, 126.6, 57.5, 37.8, 37.3, 33.6, 20.9, 18.4.Yield: 81%; pale oil; 1 H-NMR (400 MHz, CDCl 3 ) δ 7.41-7.38 (m, 2H), 7.30-7.28 (m, 2H), 7.20-7.18 (m, 3H), 7.14-7.12 (m, 2H), 3.39 ( d, J = 12.4 Hz , 1H), 3.28 (d, J = 12.4 Hz , 1H), 2.68-2.64 (M, 1H), 2.37-2.15 (m, 6H), 1.98-1.90 (m, 1H), 1.83 -1.71 (m, 1H); 13 C-NMR (100 MHz, CDCl 3 ) δ 218.0,137.2, 135.3, 132.5, 131.0, 129.4, 128.9, 126.7, 126.6, 57.5, 37.8, 37.3, 33.6, 20.9, 18.4.

[실시예 3][Example 3]

실시예 1 중 [화학식 1] 이외에는 실시예 1과 동일한 방법으로 진행하여 상기 [표1]의 화합물(3b)를 얻었다.The compound (3b) of [Table 1] was obtained in the same manner as in Example 1 except for [Formula 1] in Example 1.

2-(4-methoxyphenyl)-2-((phenylselanyl)methyl)cyclopentanone (3c)2-(4-methoxyphenyl)-2-((phenylselanyl)methyl)cyclopentanone (3c)

Figure pat00009
Figure pat00009

Yield: 85%; yellow oil; 1H-NMR (400 MHz, CDCl3) δ 7.40-7.37 (m, 2H), 7.33-7.31 (m, 2H), 7.20-7.17 (m, 3H), 6.86-6.82 (m, 2H), 3.78 (s, 3H), 3.39 (d, J = 12.4 Hz, 1H), 3.27 (d, J = 12 Hz, 1H), 2.67-2.62 (m, 1H), 2.39-2.18 (m, 3H), 1.99-1.89 (m, 1H), 1.84-1.73 (m, 1H); 13C-NMR (100 MHz, CDCl3) δ 218.0, 158.8, 132.6, 131.0, 130.1, 128.9, 127.9, 126.8, 114.0, 57.0, 55.2, 38.0, 37.3, 33.7, 18.4.Yield: 85%; yellow oil; 1 H-NMR (400 MHz, CDCl 3 ) δ 7.40-7.37 (m, 2H), 7.33-7.31 (m, 2H), 7.20-7.17 (m, 3H), 6.86-6.82 (m, 2H), 3.78 ( s, 3H), 3.39 (d, J = 12.4 Hz , 1H), 3.27 (d, J = 12 Hz, 1H), 2.67-2.62 (m, 1H), 2.39-2.18 (m, 3H), 1.99-1.89 (m, 1H), 1.84-1.73 (m, 1H); 13 C-NMR (100 MHz, CDCl 3 ) δ 218.0, 158.8, 132.6, 131.0, 130.1, 128.9, 127.9, 126.8, 114.0, 57.0, 55.2, 38.0, 37.3, 33.7, 18.4.

[실시예 4][Example 4]

실시예 1 중 [화학식 1] 이외에는 실시예 1과 동일한 방법으로 진행하여 상기 [표1]의 화합물(3d)를 얻었다.The compound (3d) of [Table 1] was obtained in the same manner as in Example 1 except for [Formula 1] in Example 1.

2-(4-fluorophenyl)-2-((phenylselanyl)methyl)cyclopentanone (3d)2-(4-fluorophenyl)-2-((phenylselanyl)methyl)cyclopentanone (3d)

Figure pat00010
Figure pat00010

Yield: 89%; yellow oil; 1H-NMR (400 MHz, CDCl3) δ 7.40-7.35 (m, 4H), 7.22-7.17 (m, 3H), 7.01-6.95 (m, 2H), 3.37 (d, J = 12.4 Hz, 1H), 3.25 (d, J = 12.4 Hz, 1H), 2.66-2.61 (m, 1H), 2.39-2.19 (m, 3H), 1.99-1.90 (m, 1H), 1.85-1.71 (m, 1H); 13C-NMR (100 MHz, CDCl3) δ 217.7, 163.0 (d, J = 245.1 Hz), 134.0, 132.8, 130.7, 129.1, 128.5 (d, J = 7.6 Hz), 126.9, 115.4 (d, J = 21 Hz), 57.1, 38.1, 37.4, 33.8, 18.4; 19F-NMR (376 MHz, CDCl3) δ -115.0.Yield: 89%; yellow oil; 1 H-NMR (400 MHz, CDCl 3 ) δ 7.40-7.35 (m, 4H), 7.22-7.17 (m, 3H), 7.01-6.95 (m, 2H), 3.37 (d, J = 12.4 Hz , 1H) , 3.25 (d, J = 12.4 Hz, 1H), 2.66-2.61 (m, 1H), 2.39-2.19 (m, 3H), 1.99-1.90 (m, 1H), 1.85-1.71 (m, 1H); 13 C-NMR (100 MHz, CDCl 3 ) δ 217.7, 163.0 (d, J = 245.1 Hz), 134.0, 132.8, 130.7, 129.1, 128.5 (d, J = 7.6 Hz), 126.9, 115.4 (d, J = 21 Hz), 57.1, 38.1, 37.4, 33.8, 18.4; 19 F-NMR (376 MHz, CDCl 3 ) δ -115.0.

[실시예 5][Example 5]

실시예 1 중 [화학식 1] 이외에는 실시예 1과 동일한 방법으로 진행하여 상기 [표1]의 화합물(3e)를 얻었다.In Example 1, except for [Formula 1], the same method as in Example 1 was carried out to obtain the compound (3e) of [Table 1].

2-(4-chlorophenyl)-2-((phenylselanyl)methyl)cyclopentanone (3e)2-(4-chlorophenyl)-2-((phenylselanyl)methyl)cyclopentanone (3e)

Figure pat00011
Figure pat00011

Yield: 77%; pale oil; 1H-NMR(400 MHz, CDCl3) δ 7.39-7.32 (m, 4H), 7.27-7.23 (m, 2H), 7.21-7.16 (m, 3H) 3.36 (d, J = 12.4 Hz, 1H), 3.25 (d, J = 12.4 Hz, 1H), 2.65-2.60 (m, 1H), 2.38-2.20 (m, 3H), 2.00-1.90 (m, 1H), 1.85-1.72 (m, 1H); 13C-NMR (100 MHz, CDCl3) δ 217.5, 136.8, 133.4, 132.8, 130.6, 129.0, 128.7, 128.3, 127.0, 57.2, 37.9, 37.4, 33.7, 18.4. Yield: 77%; pale oil; 1 H-NMR (400 MHz, CDCl 3 ) δ 7.39-7.32 (m, 4H), 7.27-7.23 (m, 2H), 7.21-7.16 (m, 3H) 3.36 (d, J = 12.4 Hz , 1H), 3.25 (d, J = 12.4 Hz, 1H), 2.65-2.60 (m, 1H), 2.38-2.20 (m, 3H), 2.00-1.90 (m, 1H), 1.85-1.72 (m, 1H); 13 C-NMR (100 MHz, CDCl 3 ) δ 217.5, 136.8, 133.4, 132.8, 130.6, 129.0, 128.7, 128.3, 127.0, 57.2, 37.9, 37.4, 33.7, 18.4.

[실시예 6][Example 6]

실시예 1 중 [화학식 1] 이외에는 실시예 1과 동일한 방법으로 진행하여 상기 [표1]의 화합물(3f)를 얻었다.The compound (3f) of [Table 1] was obtained in the same manner as in Example 1 except for [Formula 1] in Example 1.

2-((phenylselanyl)methyl)-2-(m-tolyl)cyclopentanone (3f)2-((phenylselanyl)methyl)-2-(m-tolyl)cyclopentanone (3f)

Figure pat00012
Figure pat00012

Yield: 86%; colorless oil; 1H-NMR (400 MHz, CDCl3) δ 7.42-7.37 (m, 2H), 7.21-7.18 (m, 6H), 7.07-7.05 (m, 1H), 3.38 (d, J = 12.4 Hz, 1H), 3.29 (d, J = 12 Hz, 1H), 2.69-2.64 (m, 1H), 2.39-2.19 (m, 6H), 2.02-1.89 (m, 1H), 1.85-1.77 (m, 1H); 13C-NMR (100 MHz, CDCl3) δ 218.0, 138.3 132.6, 131.1, 128.9, 128.5, 128.2, 127.4, 126.8, 123.6, 57.8, 37.7, 37.4, 33.7, 21.6, 18.4.Yield: 86%; colorless oil; 1 H-NMR (400 MHz, CDCl 3 ) δ 7.42-7.37 (m, 2H), 7.21-7.18 (m, 6H), 7.07-7.05 (m, 1H), 3.38 (d, J = 12.4 Hz, 1H), 3.29 (d, J = 12 Hz, 1H), 2.69-2.64 (m, 1H), 2.39-2.19 (m, 6H), 2.02-1.89 (m, 1H), 1.85-1.77 (m, 1H); 13 C-NMR (100 MHz, CDCl 3 ) δ 218.0, 138.3 132.6, 131.1, 128.9, 128.5, 128.2, 127.4, 126.8, 123.6, 57.8, 37.7, 37.4, 33.7, 21.6, 18.4.

[실시예 7][Example 7]

실시예 1 중 [화학식 1] 이외에는 실시예 1과 동일한 방법으로 진행하여 상기 [표1]의 화합물(3g)를 얻었다.In Example 1, except for [Chemical Formula 1], the same method as in Example 1 was carried out to obtain a compound (3 g) of [Table 1].

2-((phenylselanyl)methyl)-2-(o-tolyl)cyclopentanone (3g)2-((phenylselanyl)methyl)-2-(o-tolyl)cyclopentanone (3g)

Figure pat00013
Figure pat00013

Yield: 69%; yellow oil; 1H-NMR (400 MHz, CDCl3) δ 7.51-7.46 (m, 2H), 7.25-7.21 (m, 3H), 7.17-7.14 (m, 2H), 7.13-7.11 (m, 2H), 3.54 (d, J = 12.8 Hz, 1H), 3.43 (d, J = 12.4 Hz, 1H), 2.59-2.54 (m, 1H), 2.50-2.42 (m, 1H), 2.38-2.28 (m, 5H), 1.96-1.88 (m, 1H); 13C-NMR (100 MHz, CDCl3) δ 219.2, 138.5 136.1, 133.1, 132.9, 131.2, 129.0, 127.5, 127.3, 127.0, 126.0, 59.0, 37.5, 35.0, 34.3, 21.8, 18.6.Yield: 69%; yellow oil; 1 H-NMR (400 MHz, CDCl 3 ) δ 7.51-7.46 (m, 2H), 7.25-7.21 (m, 3H), 7.17-7.14 (m, 2H), 7.13-7.11 (m, 2H), 3.54 ( d, J = 12.8 Hz, 1H), 3.43 (d, J = 12.4 Hz, 1H), 2.59-2.54 (m, 1H), 2.50-2.42 (m, 1H), 2.38-2.28 (m, 5H), 1.96-1.88 (m, 1H); 13 C-NMR (100 MHz, CDCl 3 ) δ 219.2, 138.5 136.1, 133.1, 132.9, 131.2, 129.0, 127.5, 127.3, 127.0, 126.0, 59.0, 37.5, 35.0, 34.3, 21.8, 18.6.

[실시예 8][Example 8]

실시예 1 중 [화학식 1] 이외에는 실시예 1과 동일한 방법으로 진행하여 상기 [표1]의 화합물(3h)를 얻었다.In Example 1, except for [Formula 1], the same method as in Example 1 was carried out to obtain the compound (3h) of [Table 1].

2-(2-fluorophenyl)-2-((phenylselanyl)methyl)cyclopentanone (3h)2-(2-fluorophenyl)-2-((phenylselanyl)methyl)cyclopentanone (3h)

Figure pat00014
Figure pat00014

Yield: 73%; yellow oil; 1H-NMR (400 MHz, CDCl3) δ 7.50-7.47 (m, 2H), 7.25-7.16 (m, 5H), 7.09-7.00 (m, 2H), 3.56 (d, J = 12.4 Hz, 1H), 3.36 (d, J = 12.8 Hz, 1H), 2.58-2.31 (m, 4H), 2.00-1.90 (m, 1H), 1.84-1.73 (m, 1H); 13C-NMR (100 MHz, CDCl3) δ 218.2, 160.8 (d, J = 246 Hz), 132.4, 131.4, 131.2, 129.2 (d, J = 9.5 Hz), 129.1, 128.7 (d, J = 3.8 Hz), 126.9, 124.1 (d, J = 3.8 Hz), 116.7 (d, J = 22.9 Hz), 56.3, 37.7, 35.3 (d, J = 4.8 Hz), 32.9, 19.1; 19F-NMR (376 MHz, CDCl3) δ -108.8.Yield: 73%; yellow oil; 1 H-NMR (400 MHz, CDCl 3 ) δ 7.50-7.47 (m, 2H), 7.25-7.16 (m, 5H), 7.09-7.00 (m, 2H), 3.56 (d, J = 12.4 Hz, 1H), 3.36 (d, J = 12.8 Hz, 1H), 2.58-2.31 (m, 4H), 2.00-1.90 (m, 1H), 1.84-1.73 (m, 1H); 13 C-NMR (100 MHz, CDCl 3 ) δ 218.2, 160.8 (d, J = 246 Hz), 132.4, 131.4, 131.2, 129.2 (d, J = 9.5 Hz), 129.1, 128.7 (d, J = 3.8 Hz ), 126.9, 124.1 (d, J = 3.8 Hz), 116.7 (d, J = 22.9 Hz), 56.3, 37.7, 35.3 (d, J = 4.8 Hz), 32.9, 19.1; 19 F-NMR (376 MHz, CDCl 3 ) δ -108.8.

[실시예 9][Example 9]

실시예 1 중 [화학식 1] 이외에는 실시예 1과 동일한 방법으로 진행하여 상기 [표1]의 화합물(3i) 얻었다.The compound (3i) of [Table 1] was obtained in the same manner as in Example 1 except for [Formula 1] in Example 1.

2-(naphthalen-2-yl)-2-((phenylselanyl)methyl)cyclopentanone (3i)2-(naphthalen-2-yl)-2-((phenylselanyl)methyl)cyclopentanone (3i)

Figure pat00015
Figure pat00015

Yield: 70%; red oil; 1H-NMR (400 MHz, CDCl3) δ 7.80-7.79 (m, 4H), 7.56.7.54 (m, 1H), 7.49-7.45 (m, 2H), 7.39-7.36 (m, 2H), 7.17-7.13 (m, 3H), 3.50 (d, J = 12.4 Hz, 1H), 3.37 (d, J = 12.4 Hz, 1H), 2.89-2.79 (m, 1H), 2.41-2.27 (m, 3H), 2.20-1.95 (m, 1H), 1.89-1.78 (m, 1H); 13C-NMR (100 MHz, CDCl3) δ 217.9, 135.7, 133.1, 132.7, 132.5, 130.9, 128.9, 128.5, 128.1, 127.4, 126.8, 126.2, 125.9, 128.5, 128.1, 127.4, 126.8, 126.2, 125.9, 124.5, 58.0, 37.6, 37.5, 33.8, 18.6.Yield: 70%; red oil; 1 H-NMR (400 MHz, CDCl 3 ) δ 7.80-7.79 (m, 4H), 7.56.7.54 (m, 1H), 7.49-7.45 (m, 2H), 7.39-7.36 (m, 2H), 7.17- 7.13 (m, 3H), 3.50 (d, J = 12.4 Hz, 1H), 3.37 (d, J = 12.4 Hz, 1H), 2.89-2.79 (m, 1H), 2.41-2.27 (m, 3H), 2.20-1.95 (m, 1H), 1.89-1.78 (m, 1H); 13 C-NMR (100 MHz, CDCl 3 ) δ 217.9, 135.7, 133.1, 132.7, 132.5, 130.9, 128.9, 128.5, 128.1, 127.4, 126.8, 126.2, 125.9, 128.5, 128.1, 127.4, 126.8, 126.2, 125.9, 124.5, 58.0, 37.6, 37.5, 33.8, 18.6.

[실시예 10][Example 10]

실시예 1 중 [화학식 1] 이외에는 실시예 1과 동일한 방법으로 진행하여 상기 [표1]의 화합물(3j)를 얻었다.The compound (3j) of [Table 1] was obtained in the same manner as in Example 1 except for [Formula 1] in Example 1.

2-benzyl-2-((phenylselanyl)methyl)cyclopentanone (3j)2-benzyl-2-((phenylselanyl)methyl)cyclopentanone (3j)

Figure pat00016
Figure pat00016

Yield: 68%; yellow oil; 1H-NMR (400 MHz, CDCl3) δ 7.52-7.47 (m, 2H), 7.29-7.19 (m, 6H), 7.12-7.10 (m, 2H) 3.10 (d, J = 16.4 Hz, 1H), 3.03 (d, J = 11.6 Hz, 1H), 2.94 (d, J = 13.2 Hz, 1H), 2.78 (d, J = 13.2 Hz, 1H), 2.26-2.18 (m, 1H), 2.08-1.97 (m, 3H), 1.80-1.70 (m, 1H), 1.50-1.42 (m, 1H); 13C-NMR (100 MHz, CDCl3) δ 221.2, 136.9, 132.7, 130.8, 130.2, 129.1, 128.3, 127.0, 126.7, 54.3, 41.9, 38.7, 35.4, 31.9, 18.5. Yield: 68%; yellow oil; 1 H-NMR (400 MHz, CDCl 3 ) δ 7.52-7.47 (m, 2H), 7.29-7.19 (m, 6H), 7.12-7.10 (m, 2H) 3.10 (d, J = 16.4 Hz , 1H), 3.03 (d, J = 11.6 Hz, 1H), 2.94 (d, J = 13.2 Hz , 1H), 2.78 (d, J = 13.2 Hz, 1H), 2.26-2.18 (m, 1H), 2.08-1.97 (m , 3H), 1.80-1.70 (m, 1H), 1.50-1.42 (m, 1H); 13 C-NMR (100 MHz, CDCl 3 ) δ 221.2, 136.9, 132.7, 130.8, 130.2, 129.1, 128.3, 127.0, 126.7, 54.3, 41.9, 38.7, 35.4, 31.9, 18.5.

[실시예 11][Example 11]

실시예 1 중 [화학식 2]로서 다이벤질 셀렌나이드를 이용한 것을 제외하고는 실시예 1과 동일한 방법으로 진행하여 상기 [표1]의 화합물(3k)를 얻었다.In Example 1, except that dibenzyl selenide was used as [Formula 2], the same method as in Example 1 was carried out to obtain the compound (3k) of [Table 1].

2-((benzylselanyl)methyl)-2-phenylcyclopentanone (3k)2-((benzylselanyl)methyl)-2-phenylcyclopentanone (3k)

Figure pat00017
Figure pat00017

Yield: 75%; yellow oil; 1H-NMR (400 MHz, CDCl3) δ 7.42-7.40 (m, 2H), 7.34 (m, 2H), 7.28-7.23 (m, 3H), 7.19-7.16 (m, 3H), 3.52 (s, 2H), 2.93 (d, J = 12.4 Hz, 1H), 2.88 (d, J = 12.4 Hz, 1H), 2.62-2.58 (m, 1H), 2.38-2.12 (m, 3H), 1.94-1.85 (m, 1H), 1.81-1.69 (m, 1H); 13C-NMR (100 MHz, CDCl3) δ 218.3, 139.1, 138.9, 128.9, 128.6, 128.4, 127.3, 126.8, 126.7, 57.6, 37.7, 33.9, 33.2, 28.6, 18.4. Yield: 75%; yellow oil; 1 H-NMR (400 MHz, CDCl 3 ) δ 7.42-7.40 (m, 2H), 7.34 (m, 2H), 7.28-7.23 (m, 3H), 7.19-7.16 (m, 3H), 3.52 (s, 2H), 2.93 (d, J = 12.4 Hz, 1H), 2.88 (d, J = 12.4 Hz , 1H), 2.62-2.58 (m, 1H), 2.38-2.12 (m, 3H), 1.94-1.85 (m, 1H), 1.81-1.69 (m, 1H) ; 13 C-NMR (100 MHz, CDCl 3 ) δ 218.3, 139.1, 138.9, 128.9, 128.6, 128.4, 127.3, 126.8, 126.7, 57.6, 37.7, 33.9, 33.2, 28.6, 18.4.

[실시예 12][Example 12]

실시예 2 중 [화학식 2]로서 다이벤질 셀렌나이드를 이용한 것을 제외하고는 실시예 2와 동일한 방법으로 진행하여 상기 [표1]의 화합물(3l)을 얻었다.The compound (3l) of [Table 1] was obtained in the same manner as in Example 2, except that dibenzyl selenide was used as [Chemical Formula 2] in Example 2.

2-((benzylselanyl)methyl)-2-(p-tolyl)cyclopentanone (3l)2-((benzylselanyl)methyl)-2-(p-tolyl)cyclopentanone (3l)

Figure pat00018
Figure pat00018

Yield: 85%; yellow oil; 1H-NMR (400 MHz, CDCl3) δ 7.29.7.13 (m, 9H), 3.55 (d, J = 3.6 Hz, 2H), 2.92 (d, J = 12.4 Hz, 1H), 2.85 (d, J = 12.4 Hz, 1H), 2.61-2.56 (m, 1H), 2.32 (s, 3H), 230-2.23 (m, 2H), 2.20-2.09 (m, 1H), 1.92-1.85 (m, 1H); 13C-NMR (100 MHz, CDCl3) δ 218.4, 139.2, 137.1, 135.8, 129.4, 129.1, 128.9, 128.4, 127.0, 126.6, 57.3, 37.6, 33.9, 33.2, 28.6, 20.9, 18.4.Yield: 85%; yellow oil; 1 H-NMR (400 MHz, CDCl 3 ) δ 7.29.7.13 (m, 9H), 3.55 (d, J = 3.6 Hz, 2H), 2.92 (d, J = 12.4 Hz, 1H), 2.85 (d, J = 12.4 Hz, 1H), 2.61-2.56 (m, 1H), 2.32 (s, 3H), 230-2.23 (m, 2H), 2.20-2.09 (m, 1H), 1.92-1.85 (m, 1H); 13 C-NMR (100 MHz, CDCl 3 ) δ 218.4, 139.2, 137.1, 135.8, 129.4, 129.1, 128.9, 128.4, 127.0, 126.6, 57.3, 37.6, 33.9, 33.2, 28.6, 20.9, 18.4.

[실시예 13][Example 13]

실시예 3 중 [화학식 2]로서 다이벤질 셀렌나이드를 이용한 것을 제외하고는 실시예 3과 동일한 방법으로 진행하여 상기 [표1]의 화합물(3m)를 얻었다.In Example 3, except that dibenzyl selenide was used as [Chemical Formula 2], the same method as in Example 3 was carried out to obtain the compound (3m) of [Table 1].

2-((benzylselanyl)methyl)-2-(4-methoxyphenyl)cyclopentanone (3m)2-((benzylselanyl)methyl)-2-(4-methoxyphenyl)cyclopentanone (3m)

Figure pat00019
Figure pat00019

Yield: 85%; yellow oil; 1H-NMR (400 MHz, CDCl3) δ 7.37-7.30 (m, 3H), 7.27-7.23 (m, 2H), 7.20-7.16 (m, 3H), 6.88-6.84 (m, 2H), 3.79 (s, 3H), 3.54 (d, J = 4.8 Hz, 2H), 2.92 (d, J = 12.8 Hz, 1H), 2.84 (d, J = 12.8 Hz, 1H), 2.59-2.54 (m, 1H), 2.37-2.09 (m, 3H), 1.91-1.82 (m, 1H), 1.81-1.70 (m, 1H);13C-NMR (100 MHz, CDCl3) δ 218.4, 158.7, 139.1, 130.6, 128.9, 128.4, 127.9, 126.6, 113.9, 56.9, 55.2, 37.6, 33.9, 33.4, 28.6, 18.4.Yield: 85%; yellow oil; 1 H-NMR (400 MHz, CDCl 3 ) δ 7.37-7.30 (m, 3H), 7.27-7.23 (m, 2H), 7.20-7.16 (m, 3H), 6.88-6.84 (m, 2H), 3.79 ( s, 3H), 3.54 (d, J = 4.8 Hz, 2H), 2.92 (d, J = 12.8 Hz, 1H), 2.84 (d, J = 12.8 Hz, 1H), 2.59-2.54 (m, 1H), 2.37-2.09 (m, 3H), 1.91-1.82 (m, 1H), 1.81-1.70 (m, 1H); 13 C-NMR (100 MHz, CDCl 3 ) δ 218.4, 158.7, 139.1, 130.6, 128.9, 128.4, 127.9, 126.6, 113.9, 56.9, 55.2, 37.6, 33.9, 33.4, 28.6, 18.4.

[실시예 14][Example 14]

실시예 4 중 [화학식 2]로서 다이벤질 셀렌나이드를 이용한 것을 제외하고는 실시예 4와 동일한 방법으로 진행하여 상기 [표1]의 화합물(3n)를 얻었다.In Example 4, except that dibenzyl selenide was used as [Formula 2], the same procedure as in Example 4 was carried out to obtain the compound (3n) of [Table 1].

2-((benzylselanyl)methyl)-2-(4-fluorophenyl)cyclopentanone (3n)2-((benzylselanyl)methyl)-2-(4-fluorophenyl)cyclopentanone (3n)

Figure pat00020
Figure pat00020

Yield: 49%; yellow oil; 1HNMR (400 MHz, CDCl3) δ 7.40-7.36 (m, 2H), 7.28-7.22 (m, 3H), 7.20-7.17 (m, 3H), 7.04-6.68 (m, 2H), 3.54 (d, J = 4.4 Hz, 2H), 2.89 (d, J = 12.4 Hz, 1H), 2.84 (d, J = 12.4 Hz, 1H), 2.58-2.50 (m, 1H), 2.32-2.25 (m, 2H), 2.20-2.12 (m, 1H), 1.93-1.84 (m, 1H), 1.80-1.71 (m, 1H); 13C-NMR (100 MHz, CDCl3) δ 218.1. 162.0 (d, J = 245.1 Hz), 138.9, 134.6, 128.9, 128.5 (d, J = 7.6 Hz), 128.4, 126.7, 115.4 (d, J = 21 Hz), 56.9, 37.7, 34.1, 33.2, 28.6, 18.4; 19F-NMR (376 MHz, CDCl3) δ -115.0.Yield: 49%; yellow oil; 1 HNMR (400 MHz, CDCl 3 ) δ 7.40-7.36 (m, 2H), 7.28-7.22 (m, 3H), 7.20-7.17 (m, 3H), 7.04-6.68 (m, 2H), 3.54 (d, J = 4.4 Hz, 2H), 2.89 (d, J = 12.4 Hz, 1H), 2.84 (d, J = 12.4 Hz, 1H), 2.58-2.50 (m, 1H), 2.32-2.25 (m, 2H), 2.20-2.12 (m, 1H), 1.93-1.84 (m, 1H), 1.80-1.71 (m, 1H); 13 C-NMR (100 MHz, CDCl 3 ) δ 218.1. 162.0 (d, J = 245.1 Hz), 138.9, 134.6, 128.9, 128.5 (d, J = 7.6 Hz), 128.4, 126.7, 115.4 (d, J = 21 Hz), 56.9, 37.7, 34.1, 33.2, 28.6, 18.4; 19 F-NMR (376 MHz, CDCl 3 ) δ -115.0.

[실시예 15][Example 15]

실시예 6 중 [화학식 2]로서 다이벤질 셀렌나이드를 이용한 것을 제외하고는 실시예 6과 동일한 방법으로 진행하여 상기 [표1]의 화합물(3o)를 얻었다.In Example 6, except that dibenzyl selenide was used as [Formula 2], the same method as in Example 6 was carried out to obtain the compound (3o) of [Table 1].

2-((benzylselanyl)methyl)-2-(m-tolyl)cyclopentanone (3o)2-((benzylselanyl)methyl)-2-(m-tolyl)cyclopentanone (3o)

Figure pat00021
Figure pat00021

Yield: 60%; 1H-NMR (400 MHz, CDCl3) δ 7.27-7.14 (m, 9H), 3.54 (s, 2H), 2.92 (d, J = 12.8 Hz, 1H), 2.87 (d, J = 12.4 Hz, 1H), 2.60-2.57 (m, 1H), 2.34 (s, 3H), 2.33-2.10 (m, 3H), 1.94-1.84 (m, 1H), 1.82-1.69 (m, 1H); 13C-NMR (100 MHz, CDCl3) δ 218.5, 139.1, 138.8, 138.2, 128.9, 128.5, 128.4, 128.1, 127.5, 126.6, 123.7, 57.6, 37.7, 34.0, 33.2, 28.6, 21.6, 18.4. Yield: 60%; 1 H-NMR (400 MHz, CDCl 3 ) δ 7.27-7.14 (m, 9H), 3.54 (s, 2H), 2.92 (d, J = 12.8 Hz, 1H), 2.87 (d, J = 12.4 Hz, 1H), 2.60-2.57 (m, 1H), 2.34 (s, 3H), 2.33-2.10 (m, 3H), 1.94-1.84 (m, 1H), 1.82-1.69 (m, 1H); 13 C-NMR (100 MHz, CDCl 3 ) δ 218.5, 139.1, 138.8, 138.2, 128.9, 128.5, 128.4, 128.1, 127.5, 126.6, 123.7, 57.6, 37.7, 34.0, 33.2, 28.6, 21.6, 18.4.

[실시예 16][Example 16]

실시예 9 중 [화학식 2]로서 다이벤질 셀렌나이드를 이용한 것을 제외하고는 실시예 9와 동일한 방법으로 진행하여 상기 [표1]의 화합물(3p)를 얻었다.The compound (3p) of [Table 1] was obtained in the same manner as in Example 9, except that dibenzyl selenide was used as [Chemical Formula 2] in Example 9.

2-((benzylselanyl)methyl)-2-(naphthalen-2-yl)cyclopentanone (3p)2-((benzylselanyl)methyl)-2-(naphthalen-2-yl)cyclopentanone (3p)

Figure pat00022
Figure pat00022

Yield: 72%; 1H-NMR (400 MHz, CDCl3) δ 7.84-7.79 (m, 4H), 7.56.7.54 (m, 1H), 7.52-7.45 (m, 2H), 7.26-7.15 (m, 5H), 3.55 (s, 3H), 3.04 (d, J = 12.8 Hz, 1H), 2.96 (d, J = 12.8 Hz, 1H), 2.75-2.71 (m, 1H), 2.41-2.20 (m, 3H), 1.99-1.90 (m, 1H), 1.86-1.72 (m, 1H); 13C-NMR (100 MHz, CDCl3) δ 218.3, 139.0, 136.2, 133.1, 132.4, 128.9, 128.5, 128.4, 128.1, 127.4, 126.7, 126.3, 126.2, 125.8, 124.6, 57.8, 37.7, 34.1, 32.9, 28.7, 18.5. Yield: 72%; 1 H-NMR (400 MHz, CDCl 3 ) δ 7.84-7.79 (m, 4H), 7.56.7.54 (m, 1H), 7.52-7.45 (m, 2H), 7.26-7.15 (m, 5H), 3.55 ( s, 3H), 3.04 (d, J = 12.8 Hz, 1H), 2.96 (d, J = 12.8 Hz, 1H), 2.75-2.71 (m, 1H), 2.41-2.20 (m, 3H), 1.99-1.90 (m, 1H), 1.86-1.72 (m, 1H); 13 C-NMR (100 MHz, CDCl 3 ) δ 218.3, 139.0, 136.2, 133.1, 132.4, 128.9, 128.5, 128.4, 128.1, 127.4, 126.7, 126.3, 126.2, 125.8, 124.6, 57.8, 37.7, 34.1, 32.9, 28.7, 18.5.

Claims (5)

하기 [화학식 3]의 구조를 갖는 베타 셀레닐 케톤 유도체 화합물.
Figure pat00023

(상기 [화학식 3]에서 R1는 C1-C3 알콕시기, 알킬기, 할로겐 원소로 치환된 아릴기이고, 특히 나프틸기, 페닐기 또는 벤질기이다. R2는 페닐기 또는 벤질기이다)
Beta selenyl ketone derivative compound having the structure of the following [Formula 3].
Figure pat00023

(In [Formula 3], R 1 is a C1-C3 alkoxy group, an alkyl group, an aryl group substituted with a halogen element, and is particularly a naphthyl group, a phenyl group, or a benzyl group. R 2 is a phenyl group or a benzyl group)
제1항에 있어서,
상기 [화학식 3]의 화합물은 아래 (1) 내지 (16)의 화합물 (3a) 내지 화합물 (3p) 중 어느 하나인 것을 특징으로 하는 베타 셀레닐 케톤 유도체 화합물
(1) 2-phenyl-2-((phenylselanyl)methyl)cyclopentanone (3a),
(2) 2-((phenylselanyl)methyl)-2-(p-tolyl)cyclopentanone (3b),
(3) 2-(4-methoxyphenyl)-2-((phenylselanyl)methyl)cyclopentanone (3c)
(4) 2-(4-fluorophenyl)-2-((phenylselanyl)methyl)cyclopentanone (3d)
(5) 2-(4-chlorophenyl)-2-((phenylselanyl)methyl)cyclopentanone (3e)
(6) 2-((phenylselanyl)methyl)-2-(m-tolyl)cyclopentanone (3f)
(7) 2-((phenylselanyl)methyl)-2-(o-tolyl)cyclopentanone (3g)
(8) 2-(2-fluorophenyl)-2-((phenylselanyl)methyl)cyclopentanone (3h)
(9) 2-(naphthalen-2-yl)-2-((phenylselanyl)methyl)cyclopentanone (3i)
(10) 2-benzyl-2-((phenylselanyl)methyl)cyclopentanone (3j)
(11) 2-((benzylselanyl)methyl)-2-phenylcyclopentanone (3k)
(12) 2-((benzylselanyl)methyl)-2-(p-tolyl)cyclopentanone (3l)
(13) 2-((benzylselanyl)methyl)-2-(4-methoxyphenyl)cyclopentanone (3m)
(14) 2-((benzylselanyl)methyl)-2-(4-fluorophenyl)cyclopentanone (3n)
(15) 2-((benzylselanyl)methyl)-2-(m-tolyl)cyclopentanone (3o)
(16) 2-((benzylselanyl)methyl)-2-(naphthalen-2-yl)cyclopentanone (3p)
According to claim 1,
The compound of [Formula 3] is a beta selenyl ketone derivative compound, characterized in that any one of the compounds (3a) to compound (3p) of (1) to (16) below
(1) 2-phenyl-2-((phenylselanyl)methyl)cyclopentanone (3a),
(2) 2-((phenylselanyl)methyl)-2-(p-tolyl)cyclopentanone (3b),
(3) 2-(4-methoxyphenyl)-2-((phenylselanyl)methyl)cyclopentanone (3c)
(4) 2-(4-fluorophenyl)-2-((phenylselanyl)methyl)cyclopentanone (3d)
(5) 2-(4-chlorophenyl)-2-((phenylselanyl)methyl)cyclopentanone (3e)
(6) 2-((phenylselanyl)methyl)-2-(m-tolyl)cyclopentanone (3f)
(7) 2-((phenylselanyl)methyl)-2-(o-tolyl)cyclopentanone (3g)
(8) 2-(2-fluorophenyl)-2-((phenylselanyl)methyl)cyclopentanone (3h)
(9) 2-(naphthalen-2-yl)-2-((phenylselanyl)methyl)cyclopentanone (3i)
(10) 2-benzyl-2-((phenylselanyl)methyl)cyclopentanone (3j)
(11) 2-((benzylselanyl)methyl)-2-phenylcyclopentanone (3k)
(12) 2-((benzylselanyl)methyl)-2-(p-tolyl)cyclopentanone (3l)
(13) 2-((benzylselanyl)methyl)-2-(4-methoxyphenyl)cyclopentanone (3m)
(14) 2-((benzylselanyl)methyl)-2-(4-fluorophenyl)cyclopentanone (3n)
(15) 2-((benzylselanyl)methyl)-2-(m-tolyl)cyclopentanone (3o)
(16) 2-((benzylselanyl)methyl)-2-(naphthalen-2-yl)cyclopentanone (3p)
아세토나이트릴 용매, n-Bu4NBF4전해질 하에서 하기 [화학식 1]의 구조를 갖는 알릴알코올 유도체(1)에 [화학식 2]의 구조를 갖는 다이셀레나이드 유도체(2)를 이용한 작용기를 도입하고 세미-피나콜 전이반응을 하기 [반응식 1]과 같이 진행하는 것을 특징으로 하는 [화학식 3]의 구조를 갖는 베타 셀레닐 케톤 유도체(3)의 제조방법.
[반응식 1]
Figure pat00024

(상기 [반응식 1]에서 상기 R1는 C1-C3 알콕시기, 알킬기, 할로겐 원소로 치환된 아릴기이고, 특히 나프틸기, 페닐기 또는 벤질기이다. R2는 페닐기 또는 벤질기이다)
In the acetonitrile solvent, n- Bu 4 NBF 4 electrolyte, a functional group using a dieselenide derivative (2) having the structure [Formula 2] is introduced into an allyl alcohol derivative (1) having the structure [Formula 1] below. Method for producing a beta-selenyl ketone derivative (3) having the structure of [Formula 3], characterized in that the semi-finacol transfer reaction proceeds as shown in [Scheme 1].
[Scheme 1]
Figure pat00024

(In [Scheme 1], R 1 is a C1-C3 alkoxy group, an alkyl group, an aryl group substituted with a halogen element, and is particularly a naphthyl group, a phenyl group, or a benzyl group. R 2 is a phenyl group or a benzyl group)
제3항에 있어서,
상기 세미-피나콜 전이반응은 유리 탄소 전극을 넣고 IKA ElectraSyn 기기에서 5 내지 10 mA의 전류로 30분 이상 2 시간미만 교반하여 이루어지는 것을 특징으로 하는 베타 셀레닐 케톤 유도체(3)의 제조방법.
According to claim 3,
The semi-finacol transfer reaction is a method of manufacturing a beta selenyl ketone derivative (3), wherein the glass carbon electrode is inserted and stirred for 30 minutes or more and less than 2 hours at a current of 5 to 10 mA in an IKA ElectraSyn device.
제3항 또는 제4항에 있어서,
상기 전류의 크기가 7 mA이고, 교반시간이 1시간인 것을 특징으로 하는 베타 셀레닐 케톤 유도체(3)의 제조방법
The method of claim 3 or 4,
Method of manufacturing a beta selenyl ketone derivative (3), characterized in that the magnitude of the current is 7 mA and the stirring time is 1 hour
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